On the origin of chaotrope-modulated electrocatalytic activity of cytochrome c at electrified aqueous|organic interfaces

Abstract

Aqueous chaotropes accelerate the electrocatalytic activity of adsorbed cytochrome c towards reactive oxygen species (ROS) production at electrified aqueous|organic interfaces.

Cover Feature: Potential‐Modulated Ion Distributions in the Back‐to‐Back Electrical Double Layers at a Polarised Liquid|Liquid Interface Regulate the Kinetics of Interfacial Electron Transfer (ChemElectroChem 3/2023)

“…A comprehensive understanding of biphasic interfacial electron transfer (IET) reactions between aqueous and organic soluble redox couples at the interface between two immiscible electrolyte solutions (ITIES) provides the fundamental foundation on which an ever-increasing range of applications are based, such as: (i) interfacial electrosynthesis of thin films of advanced functional materials, e. g., conducting polymers; [1] (ii) interfacial redox electrocatalysis of energy conversion and storage (ECS) reactions, e. g., the biphasic H 2 evolution reaction (HER), O 2 reduction reaction (ORR) and O 2 evolution reaction (OER); [2][3][4] (iii) interfacial bioelectrochemistry of proteins, e. g., cytochrome c, to replicate the molecular machinery of biomembranes; [5,6] and (iv) interfacial photoconversion reactions involving porphyrins towards artificial photosynthesis. [7][8][9][10] The modified Verwey-Niessen (MVN) model describes the nature of the electric double layer (EDL) at the ITIES.…”

Potential‐Modulated Ion Distributions in the Back‐to‐Back Electrical Double Layers at a Polarised Liquid|Liquid Interface Regulate the Kinetics of Interfacial Electron Transfer

“…A comprehensive understanding of biphasic interfacial electron transfer (IET) reactions between aqueous and organic soluble redox couples at the interface between two immiscible electrolyte solutions (ITIES) provides the fundamental foundation on which an ever-increasing range of applications are based, such as: (i) interfacial electrosynthesis of thin films of advanced functional materials, e. g., conducting polymers; [1] (ii) interfacial redox electrocatalysis of energy conversion and storage (ECS) reactions, e. g., the biphasic H 2 evolution reaction (HER), O 2 reduction reaction (ORR) and O 2 evolution reaction (OER); [2][3][4] (iii) interfacial bioelectrochemistry of proteins, e. g., cytochrome c, to replicate the molecular machinery of biomembranes; [5,6] and (iv) interfacial photoconversion reactions involving porphyrins towards artificial photosynthesis. [7][8][9][10] The modified Verwey-Niessen (MVN) model describes the nature of the electric double layer (EDL) at the ITIES.…”